Article https://doi.org/10.

1038/s41467-023-36524-x

Microwave-assisted design of nanoporous

graphene membrane for ultrafast and
switchable organic solvent nanofiltration
Received: 31 August 2022 Junhyeok Kang1, Yeongnam Ko2, Jeong Pil Kim1, Ju Yeon Kim1, Jiwon Kim1,
Ohchan Kwon1, Ki Chul Kim 2 & Dae Woo Kim 1
Accepted: 2 February 2023

Layered two-dimensional materials can potentially be utilized for organic

Check for updates solvent nanofiltration (OSN) membrane fabrication owing to their precise
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molecular sieving by the interlayer structure and excellent stability in harsh

conditions. Nevertheless, the extensive tortuosity of nanochannels and bulky
solvent molecules impede rapid permeability. Herein, nanoporous graphene
(NG) with a high density of sp2 carbon domain was synthesized via sequential
thermal pore activation of graphene oxide (GO) and microwave-assisted
reduction. Due to the smooth sp2 carbon domain surfaces and dense nano-
pores, the microwave-treated nanoporous graphene membrane exhibited
ultrafast organic solvent permeance (e.g., IPA: 2278 LMH/bar) with excellent
stability under practical cross-flow conditions. Furthermore, the membrane
molecular weight cut-off (MWCO) is switchable from 500 Da size of molecule
to sub-nanometer-size molecules depending on the solvent type, and this
switching occurs spontaneously with solvent change. These properties indi-
cate feasibility of multiple (both binary and ternary) organic mixture separa-
tion using a single membrane. The nanochannel structure effect on solvent
transport is also investigated using computation calculations.

Chemical purification is a crucial process in various industries, such
as petrochemicals and pharmaceuticals, to purify valuable products
and recycle solvents or catalysts1. Conventional purification pro-
cesses based on distillation and crystallization are costly and inap-
plicable for heat-sensitive products2. Alternatively, organic solvent
nanofiltration (OSN) membranes capable of separating molecules
between 100–2000 Da in size are promising owing to their envir-
onmentally friendly operation, high energy efficiency, and integrated
system3,4. Specifically, when the membrane has switchable molecular
separation properties by external stimuli or chemical conditions, the
OSN-based separation process can be further integrated and made
cost-effective because most practical chemical purification pro-
cesses aim to separate multiple mixed molecules. As a proof of
concept, few membranes with switchable molecular separation
properties have been demonstrated using covalent organic networks
(CON), porous organic cages (POC), metal-organic frameworks
(MOF), and functionalized graphene5–8.
Graphene and its derivatives are the most widely utilized two-
dimensional (2D) materials for membrane fabrication, which has
been widely applied to separation applications such as gas separa-
tion, water treatment, organic solvent purification, pervaporation,
and nanofiltration9–15. Particularly, graphene oxide (GO) is effective
for membrane fabrication because large-scale fabrication is feasible
via practical continuous coating methods (bar or slot-die coating)
and its narrow interlayer spacing enables precise molecular
separation11,16,17. However, narrow interlayer spacing and lengthy
diffusion pathways typically result in limited organic solvent flow18.
Therefore, various approaches have been reported to modify nano-
channel structure, such as pore generation, flake size control, and
hybridization with other nanomaterials, which can decrease solvent

1
Department of Chemical and Biomolecular Engineering, Yonsei University, Yonsei-ro 50, Seodaemun-gu Seoul (03722), Republic of Korea. 2Department of
Chemical Engineering, Konkuk University, Seoul 05029, Republic of Korea. e-mail: audw1105@yonsei.ac.kr

Nature Communications | (2023)14:901 1

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diffusion length or increase nanochannel size18–20. While these
methods can produce OSN membrane with rapid solvent permea-
tion, switchable molecular separation phenomena have been rarely
reported and the majority of membranes have been utilized to
separate single or binary mixtures18,21.
Herein, nanoporous graphene with rich sp2 carbon domains were
prepared for OSN membrane fabrication. Dense nanopores on the
basal plane of graphene were activated by spontaneous thermal
annealing of GO. Subsequently, microwave treatment was conducted
to increase the proportion of sp2 carbon domains by transforming
defective sp3 carbons at elevated local temperatures. Graphitic struc-
tural changes owing to thermal activation and microwave treatment
were systemically investigated. The membrane OSN performances
were investigated using a dead-end and cross-flow system. Further-
more, molecular separation properties of microwave-treated nano-
porous graphene (MNG) membrane were demonstrated to be
switchable in response to the solvents employed to separate multiple
mixtures of subnanometer-sized organic molecules through repetitive
solvent exchange and filtration using a single membrane.
Results
Fabrication of microwave-treated NG membrane
Figure 1a depicts the overall fabrication procedure for MNG mem-
branes. First, to prepare nanoporous graphene (NG), the as-prepared
GO powder was thermally annealed at 200 °C for 5 min under ambient
conditions, which activates numerous nanopores on the graphene
surface by decomposing oxygen-containing groups22. Thermal
annealing is effective at producing dense nanopores; however, oxygen
group decomposition frequently results in amorphous sp3 carbon
formation. Because the sp3 carbon structure may impede solvent
molecule transport owing to steric hindrance23,24, NG was treated with
microwave to recover sp2 domains on the graphene surface25. Voiry
et al. reported that high-quality graphene composed with a high pro-
portion of sp2 carbons can be prepared via treating reduced graphene
oxide with microwave25, while microwave treatment effects on nano-
porous graphene have been not investigated. In addition, the micro-
Fig. 1 | Microwave-assisted design of nanoporous graphene membrane. a Preparation of sp2 carbon enriched nanoporous multilayer graphene membrane enabled by
microwave-assisted reduction. b Membrane working principle for switchable molecular separation in response to solvent types.
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wave treatment can generate denser nanopores during sp3 carbon
rearrangement or decomposition, further enhancing solvent permea-
tion. Notably, previous chemical and thermal reduction methods uti-
lized for graphene membranes solely remove oxygen-containing
groups with partial recovery of sp2 domains because recrystallization
of amorphous carbons require extremely high temperatures above
2000 °C25–27. Furthermore, as thermally activated nanoporous gra-
phene is extremely defective, conventional thermal and chemical
reduction methods are inapplicable. In contrast, the microwave
treatment is effective at recrystallizing the sp3 carbon structure by
increasing the local temperature of graphene owing to its explosive
carrier scattering under microwave irradiation28.
The prepared MNG powder was dispersed in 1-methyl-2-
pyrrolidone (NMP) via sonication. After removing large particles and
unexfoliated flakes by centrifugation, the MNG solution was vacuum
filtered on nylon support. Figure 1b illustrates the nanochannel
structures of MNG membrane. The dense nanopore can effectively
provide additional flow channels and filter large molecules. Owing to
sp2 domain recovery after microwave treatment, the MNG membrane
can possess a narrower interlayer spacing than the NG membrane, and
the remaining sp3 carbons serve as spacers to support stacked gra-
phene sheets. In addition, the nanochannel size of the MNG membrane
is spontaneously variable based on the swelling degree of organic
solvents within the MNG layer, resulting in switchable molecular
separation phenomena, which is subsequently described in detail.
Figure 2a, b depicts the SEM images of MNG particles and exfo-
liated nanosheet, respectively. As-prepared GO sheets were densely
stacked, whereas the NG layers were expanded during thermal acti-
vation by CO and CO2 gas emissions (Supplementary Fig. 1)18. The
expanded graphene layers maintained a hierarchical structure after
microwave treatment, but frequent porous defects were observed on
the graphene surface, which can be attributed to the decomposition of
oxygen-containing groups and sp3 carbons caused by microwave-
induced local high temperatures (Fig. 2a). Figure 2b illustrates that
the exfoliated MNG flake exhibits a lateral size of several hundred
nanometers and a thickness of ~6 nm, revealed using atomic force
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Fig. 2 | Structure of sp2-enriched nanoporous graphene and its membrane.
a, b SEM images of MNG particle and exfoliated nanosheet. c AFM image of MNG
nanosheet and its height profile. d, e HR-TEM images of MNG. f Corresponding
selected area electron diffraction (SAED) pattern of MNG obtained from d. g TEM
microscopy (AFM) and corresponding height profile (Fig. 2c). Strong
inter-sheet connections via van der Waals interaction or generation of
intersheet chemical bonding appear to impede single-layer exfoliation
of MNG sheets, which were mostly produced as multilayered
sheets29,30. In optimizing microwave strength, more defects were
observed to appear on the graphene plane with increasing microwave
power (Supplementary Fig. 2) and 700 W was selected as the optimal
condition to generate dense nanopores and restore sp2 domains. The
treatment duration was maintained within a few seconds to preserve
the graphene structure, which would otherwise burn.
As illustrated in Fig. 2d–f, high-resolution TEM images, and cor-
responding SAED and atomic mapping images were acquired to
directly visualize the crystalline structure of the MNG flake. Although
GO possessed numerous oxidized regions with partial sp2 regions, the
oxidized regions were eliminated after thermal activation (Supple-
mentary Fig. 3). However, because the activation temperature (200 °C)
is too low to induce recrystallization of sp3 carbon, amorphous sp3
regions were observed and low crystallinity was confirmed by the
broad hexagonal SAED pattern in Supplementary Fig. 3. On the other
hand, the TEM images of MNG (Fig. 2d) show abundant nanopores and
the high-resolution TEM image (Fig. 2e) reveals a hexagonal lattice
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and corresponding EDS mapping images. The numbers represent the atomic
weight percentages. h, i Photographic images of MNG dispersion in NMP at 0.5 mg/
mL of concentration and MNG membrane. j, k Top-view and cross-sectional SEM
images of MNG membrane on nylon support.
structure of graphene, indicating the recovery of sp2 carbon bonds
from amorphous sp3 carbons following microwave treatment. Sharp
hexagonal patterns in the corresponding SAED pattern of MNG cor-
roborate the microwave-induced transformation of sp2 domains
(Fig. 2f). However, the SAED pattern is not as sharp as that of graphite
or single-layer graphene grown by chemical vapor deposition owing to
dense nanopore formation31. Energy dispersive spectroscopy (EDS)
mapping images for carbon and oxygen (Fig. 2g) further demonstrate
that oxygen groups were effectively eliminated by microwave treat-
ment, as evidenced by the low oxygen quantities (3%).
Figure 2h depicts a photograph of the MNG solution dispersed in
NMP at a concentration of 0.5 mg/mL using sonication and cen-
trifugation. The MNG solution was filtered on commercial nylon sup-
ports (200 nm pore size) to fabricate membranes (Fig. 2i). Because of
the high degree of reduction, the membrane color was as dark as
graphite paper. Figure 2j, k displays the SEM images of uniform MNG
layers with 200 nm thickness. Defective structures such as cracks and
aggregated particles were undetected. In addition, the membrane was
flexible and delamination of graphene layer was not observed as
shown in the bending test (Supplementary Fig. 4), indicating good
adhesion between graphene and polymer support.
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Fig. 3 | Chemical structure of graphene materials. a XPS survey scan, and b corresponding atomic percentage of GO, NG, MNG, CrGO, and MCrGO. c XPS C1s spectra and
d Raman spectra of GO, NG, MNG, CrGO, and MCrGO. Raman spectra were measured using an excitation wavelength of 532 nm.
Effect of pore structure on the degree of microwave reduction
XPS and Raman spectroscopy investigation were conducted to analyze
the effects of pore activation and microwave treatment on the crys-
talline structure of nanoporous graphene (Fig. 3). First, the chemical
structures of graphene materials were investigated using XPS as
depicted in Fig. 3a–c and Supplementary Fig. 5. The XPS survey scan
and corresponding atomic percentage of samples (Fig. 3a, b) exhibit a
reduced oxygen atomic percentage from 30.2% for GO to 7.9% for
MNG due to the sequential thermal and microwave treatments. Che-
mically reduced graphene oxide (CrGO) with hydrazine exhibited a
reduced oxygen atomic percentage of 14.2%, which further decreased
to 5.3% after microwave treatment (MCrGO, microwave-treated che-
mically reduced graphene oxide). MNG has a slightly greater oxygen
atomic percentage than MCrGO because NG comprised of a defective
porous structure that is difficult to recrystallize. In addition, defective
graphene is well known to exhibit low electrical conductivity, which
may decrease the local temperature of graphene under microwave
irradiation28.
The chemical bonds of graphene were further investigated as
depicted in XPS C1s spectra in Fig. 3c and Supplementary Figure 5. GO
exhibits oxygen-containing groups at C–O (285.9 eV), C = O (287.5 eV),
and COOH (289.8 eV). Due to the decomposition of oxygen-containing
groups, the C–O peak intensity significantly decreased after the first
thermal annealing. The dominant C–C peak of MNG, generated from a
defective amorphous carbon structure, was observed after microwave
treatment. While the C1s spectrum shape of CrGO is similar to that of
MNG, CrGO, and MCrGO primarily exhibited a C–C peak and an
additional C–N (284.6 eV) peak originated from hydrazine. As shown in
Fig. 3a, the atomic nuclei scans reveal low amounts of oxygen-
containing groups in MCrGO, reconfirming a higher degree of reduc-
tion than MNG. The reduction of oxygen-containing groups was fur-
ther confirmed by the FT-IR spectra (Supplementary Figs. 6–7),
revealing the significantly decreased peak intensities related to
oxygen-containing groups after thermal activation and microwave
treatment. As depicted in Supplementary Fig. 6b, the peak intensities
decreased with increasing microwave power owing to the enhanced
decomposition of oxygen-containing groups at higher local tempera-
tures. The low weight loss of MNG and MCrGO during the TGA test
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further validates the substantial reduction degree of graphene with
microwave treatment (Supplementary Fig. 8), indicating the sup-
pressed thermal decomposition of graphenes after microwave treat-
ment. The contact angles of solvents (Supplementary Fig. 9) exhibited
enhanced hydrophobic and oleophilic properties of the MNG mem-
brane than graphene oxide owing to the low proportion of oxygen-
containing groups.
Raman spectroscopy was employed to investigate the crystalline
structure (Fig. 3d) because the presence of sharp D, G, and 2D bands
straightforwardly indicates the presence of long-range ordered sp2
carbon domains32. While directly visualized TEM images in Fig. 2 con-
firm the presence of ordered carbon crystals, the relatively large beam
size (several micrometers in diameter) of Raman spectroscopy is more
informative and reveals the crystal structure on a large scale. The D-
band/G-band intensity ratio decreased from 1.02 for GO to 0.94 for NG
owing to the decomposition of oxygen-containing groups following
thermal activation. The broad D-band width of NG indicates amor-
phous sp3 carbon formation33. However, the Raman spectrum of MNG
(shown in green) reveals a sharp D-band and the existence of a 2D peak,
indicating sp2 carbon recovery by microwave treatment25. Interest-
ingly, the D/G intensity ratio of MNG significantly increased to 1.57
owing to dense nanopore formation and high concentration of carbon
edges in nanopores34,35. The spectra shapes are identical to that of
nanoporous graphene produced by etching CVD graphene with
plasma or ion beam exposure35. The D-band intensity increased with
increasing microwave power, possibly owing to the enhanced gen-
eration of defective pores (Supplementary Fig. 10). The D/G intensity
ratio of MNG is remarkably higher and the 2D peak intensity is lower
than that of MCrGO, indicating that the NG pore structure hinders
carbon crystallization compared to CrGO36. Because GO is unreactive
towards microwave owing to its insulation properties, a comparison
with neat GO was not performed. Moreover, the average size of sp2
domains was estimated using the Raman spectra of the samples
(Supplementary Fig. 11)37. The sp2 crystallite size of MNG was calcu-
lated to be 13.5 nm, which is less than the size of GO (19.1 nm) and NG
(20.7), implying that the sp2 domain size decreased throughout the
thermal annealing and microwave treatment, despite the increasing
density of sp2 domains.
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Fig. 4 | Interlayer structure of graphene materials. a Normalized XRD patterns of
GO, NG, MNG, CrGO, and MCrGO. b XRD patterns of MNG membrane after
immersion in various solvents. c Schematic structure of MNG membrane in dry-
Nanopore generation was also confirmed by N2 adsorption–
desorption isotherms and corresponding pore size distribution (PSD)
by Barrett–Joyner–Halenda (BJH) model (Supplementary Fig. 12 and
Supplementary Table 1). Significant N2 adsorption by NG at relative
pressures <0.1 indicates the presence of micropores38. MNG adsorbs
more N2 than NG, and the PSD reveals MNG pore size to be <3 nm.
Furthermore, the Brunauer–Emmett–Teller (BET) surface area
increased from 306 m2/g for NG to 419 m2/g for MNG. These results
indicate additional nanopore formation by microwave treatment.
Based on the preceding observations, it is concluded that nanoporous
graphene with high crystallinity can be successfully prepared using
sequential thermal activation and microwave treatment, notwith-
standing the presence of a small proportion of sp3 carbon or oxygen.
Interlayer structure and swelling behavior in solvents
X-ray diffraction (XRD) patterns were obtained from graphene films to
elucidate the interlayer structure of graphene after thermal activation
and microwave treatment, as depicted in Fig. 4a. The d-spacing
reduced from 8.3 Å for GO to 3.6 Å for NG owing to the removal of
oxygen-containing groups after thermal activation18. The NG diffrac-
tion peak is broader than that of graphite owing to the less-ordered
structure of NG resulting from the presence of amorphous sp3 carbons
on the graphene plane18. After microwave treatment, the d-spacing of
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state and after swelling in a good solvent. d–g Cross-sectional HR-TEM images of
NG (d, e) and MNG (f, g), respectively, and corresponding FFT images.
MNG (~3.5 Å) reduced below that of NG (3.6 Å) owing to enhanced
reduction and increased crystallinity, and the d-spacing remained
identical regardless of microwave power (Supplementary Fig. 13). Due
to the presence of both sp2 regions and sp3 regions in the basal plane of
MNG, a diffraction peak of MNG is considered to be composed of two
patterns: defective region stacking and pi-pi stacking of sp2 regions39.
This assumption is corroborated by the MCrGO peak, which exhibits a
less broad and right-shifted pattern because MCrGO is primarily
structured with sp2 carbons resulting from a higher degree of reduc-
tion and the absence of dense nanopores.
The XRD patterns in solvents were further analyzed to determine
the interlayer spacing variations in the MNG membrane in response to
solvent type (Fig. 4b). The d-spacing values of the MNG membrane are
similar in water, ethanol, and IPA, which are known to be poor solvents
for graphene dispersion, and these values are near to that of the MNG
membrane in the dry state. In contrast, the d-spacing value was sig-
nificantly increased in NMP which is a well-known good solvent for
graphene dispersion40. The interlayer spacing variation in solvents is
illustrated in Fig. 4c. The MNG membrane exhibits a combined struc-
ture with defective sp3-stacked regions and graphitic sp2-stacked
regions. Particularly, the spacing composed of defective sp3 regions is
more easily intercalated by solvent molecules than the narrow spacing
of sp2 regions. Therefore, the interlayers may further swell in good
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Fig. 5 | Organic solvent nanofiltration performance of MNG membrane.
a Permeance of pure organic solvents across 200 nm thick NG and MNG mem-
branes as a function of viscosity. b–d Nanofiltration performance of MNG mem-
branes tested with several organic solvents and dye molecules including methylene
solvents. In contrast, the interlayer structure with sp2-stacked regions
could be rigidly maintained owing to the pi–pi interactions of sp2
regions, which is crucial for fabricating stable membranes in solvents.
As depicted in Fig. 4d–g, cross-sectional HR-TEM images of the
MNG membrane were obtained to reveal its interlayer structure. Both
samples were prepared using the focused ion beam technique. The
TEM images of both NG and MNG membranes depict the stacked
graphene layers; however, the MNG membrane exhibits better aligned
and compactly stacked graphene layers. The enhanced ordered
structure of the MNG membrane was further confirmed by the FFT
patterns denoted by yellow arrows, indicating a broader arc pattern
from the NG sample with larger d-spacing.
OSN performance of MNG membrane in various solvents
The membrane was tested as depicted in Fig. 5 to estimate the nano-
filtration performance of the MNG membrane in various organic
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blue (MnB), rhodamine B (RhB), acid red 1 (AR), congo red (CR), methyl blue (MB),
brilliant blue G (BBG), and evans blue (EB) at 3 bar: IPA (b), ethanol (c), NMP (d).
e Comparison of IPA nanofiltration performances. All data points were averaged
from at least three samples.
solvents. The permeance of various pure organic solvents was initially
evaluated (Fig. 5a and Supplementary Table 2) at 3 bar using the
200 nm thick NG and MNG membranes (Fig. 2k and Supplementary
Fig. 14). The MNG membrane demonstrated ultrafast permeances for
various organic solvents, ranging from 13117 LMH/bar for acetone to
1300 LMH/bar for 1-butanol, which are surprisingly near to the solvent
permeances of a bare nylon support. In summary, the solvent per-
meance was inversely proportional to the solvent viscosity. The sol-
vent permeance in 2D lamellar membranes can be calculated
theoretically by using classical Hagen-Posieuile (HP) equation41. The
permeance of MNG membrane (2278 LMH/bar of IPA) is exceptionally
higher than the theoretical values as shown in Supplementary Fig. 15. A
possible reason can be the smoother surface of highly reduced nano-
porous graphene with dense sp2 carbon regions, making the transport
of ordered solvent molecules easier in the nanochannels. In addition,
low friction at graphene surface by low oxygen groups and sp2 regions
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can be favorable for the solvent transport, as observed in the fast water
transport through supported graphene nanochannel41,42.
Remarkably, toluene and water exhibited relatively low per-
meance. The low permeance of toluene is expected to arise from the
large molecular size of toluene, resulting in hindered transport within
the interlayers43. Moreover, a lower water flux than other solvents
could result from the hydrophobic surface of MNG, which is unfa-
vorable to water sorption. Several previous studies had either expec-
ted the selective permeation of alcohol or nonpolar solvent through
hydrophobic nanoporous graphene channels44, or the promotion of
hydrogen bonding with water by residual oxygen-containing groups,
thereby hindering water molecule diffusion45,46. In addition, it is
emphasized that the MNG membrane exhibited significantly higher
permeances than the NG membrane owing to the increased produc-
tion of nanopores and the smoother surface comprised of dense sp2
carbon regions. Detailed mechanisms of enhanced organic solvent
transport in graphene nanochannel are subsequently discussed herein
using computational simulations.
Figure 5b–d illustrates the OSN performance of the MNG mem-
brane in IPA, ethanol, and NMP with probe dye molecules ranging in
size from 300 to 1000 Da. The tests were conducted at 3 bar and
10 mg/L of dye concentration (Supplementary Fig. 16). As depicted in
Fig. 5b, the MNG membrane exhibited nearly 100% high rejection rates
for EB (961 Da), CR (697 Da), and AR (509 Da), whereas smaller mole-
cules exhibited lower rejection rates such as RhB (479 Da, 50.5%) and
MnB (320 Da, 20.7%). The NG membrane demonstrated lower rejec-
tion rates than the MNG membrane below 600 Da, such as AR (84.6%),
RhB (31.5%), and MnB (18.1%), indicating the enhanced rejection per-
formance by the better ordered and narrower interlayers of MNG. The
MNG membrane was evaluated in ethanol and NMP under identical
conditions (Fig. 5c, d). Interestingly, the MWCO of the MNG membrane
increased from 509 Da to 800 Da in ethanol; furthermore, the MNG
membrane exhibited low rejection rates below 20% for all dyes in NMP.
Because the membrane exhibited stability in NMP, membrane damage
cannot account for the low rejection rate (Supplementary Fig. 17).
According to the XRD patterns of swollen MNG membranes, the low
rejection rates in ethanol and NMP may be attributable to the enlarged
interlayer spacing in ethanol and NMP (Fig. 4b). Moreover, the smaller
effective/solvated diameters of dyes in ethanol can cause low rejection
rates47. These results indicate that the separation performance of MNG
membrane can be altered in response to different solvent types. In
addition to the aforementioned solvents, we also tested MNG mem-
branes with acetone and methanol, which are also one of the most
widely used solvents in organic chemistry (Supplementary Fig. 18).
MWCO was around 450 Da in acetone and around 750 Da in methanol.
We also confirmed that the retentate was concentrated after filtration
due to the filtered dyes on feed side, indicating that the rejection
occurred by molecular sieving rather than adsorption (Supplemen-
tary Fig. 19).
The OSN performance of the MNG membrane was compared to
that of prior OSN membranes using the upper bound based on pure
IPA permeance and MWCO (Fig. 5e and Supplementary Table 3). The
MNG membrane exhibited an ultrafast pure IPA permeance of 2278
LMH/bar and the MWCO of 509 Da, which significantly exceeded the
upper bound of previously reported OSN membranes. In addition, the
MNG membrane performance in ethanol was compared to that of
other OSN membranes (Supplementary Fig. 20 and Supplementary
Table 4) and the MNG membrane stability was verified using an
immersion test and long-term filtration test under cross-flow condi-
tions (Supplementary Figs. 21–25). For 30 days, the MNG membrane
proved extremely stable in various solvents including water, IPA, acid,
and alkaline solutions (Supplementary Fig. 21). Furthermore, the
membrane exhibited extremely stable rejection rates (>99%) for two
days during the cross-flow filtration test (Supplementary Figs. 22–25),
which is achieved by strong pi–pi interaction between MNG flakes.
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Moreover, any crack on the membrane surface was not observed after
the filtration test even though a dye cake was formed due to the fast
solvent permeance (Supplementary Fig. 24). In addition, the mem-
brane showed excellent diafiltration performance with binary mixed
dye mixture feed under cross-flow conditions, maintaining high
rejection rates of EB above >99%, while Methyl orange (MO) rejection
rate was ~0% (Supplementary Fig. 25).
Multiple mixture separation by MNG membrane
To explore the feasibility of separation for mixed molecules, binary
mixture separation tests were conducted using the MNG membrane
under a dead-end condition (Fig. 6 and Supplementary Fig. 26). The
test was conducted at 3 bar with a total concentration of 1000 ppm in
IPA for the binary feed solution. The feed solution was filtered through
the MNG membrane, following which the retentate was re-dispersed
and re-filtrated. The process was repeated several times to perfectly
separate the binary mixture (Fig. 6a). After initial filtering, the yellow
solution (MO, 327 Da) was permeated without the dark red solution
(AR, 509 Da), and the re-dispersed retentate solution darkened as the
yellow solution of MO was completely extracted (Fig. 6b). In the UV–Vis
spectra (Fig. 6c–e and Supplementary Fig. 27), while the mixed feed
solution contains two absorbance peaks of AR and MO (Fig. 6c), the
permeate solutions exhibited a single peak of smaller MO by the fifth
cycle (Fig. 6e). Furthermore, the re-dispersed retentate solution only
exhibited a peak corresponding to larger AR after the fifth cycle, indi-
cating the successful separation of most smaller MO molecules and the
concentration of larger AR molecules based on size exclusion using the
MNG membrane (Fig. 6d). Figure 6f, g exhibits the purity and con-
centration of AR and MO in feed and permeate side after each filtration
cycle, indicating the separation of highly concentrated AR and MO with
a high purity of nearly 100% on each side after five cycles of filtration.
Most importantly, due to the ultrafast solvent permeance of the MNG
membrane, a single filtration of 100 mL of solution was completed
within a minute, indicating that the operation efficiency can be sig-
nificantly greater than conventional OSN membranes or distillation.
A membrane with switchable molecular separation properties is
verily required to purify multiple mixtures with single equipment
because separation processes can be accomplished without
membrane replacement. To demonstrate the switchable molecular
separation property of the MNG membrane, the filtration test was
conducted at 3 bar with a feed of ternary dye mixtures containing MO
(327 Da), AR (509 Da), and EB (961 Da) in IPA (Fig. 7) and the separation
was conducted by solvent exchange to exploit the solvent-dependent
switchable interlayer structure of MNG (Fig. 7a). The brown feed
solution exhibits three absorbance peaks of MO, AR, and EB as shown
in Fig. 7b. After the initial filtration, the yellow solution (MO) was
permeated with only the MO absorbance peak as MO is below the
509 Da of MWCO in IPA. During the second filtration, the pink solution
(AR) was permeated with an AR peak as AR is below the 800 Da of
MWCO in ethanol. Finally, the blue solution (EB) was completely per-
meated in NMP with an EB peak, demonstrating that the ternary
molecular mixtures were successfully separated by solvent exchange
with the MNG membrane. Furthermore, the filtration process was
repeated with the ternary mixture feed solution to confirm the rever-
sible switching properties. The MNG membrane exhibited the same
result after the second test as depicted in the UV–Visible absorbance
spectra and photo images of permeate solutions. The cycle test con-
firmed that the interlayer structure of the MNG membrane is switch-
able based on the solvents and that the separation performance is
reversible. For polymeric membranes, the changes of MWCO by
swelling of polymer in organic solvents have been widely reported.
However, the MWCO changes of polymeric membranes are normally
not fast and not precise as we are reporting with our graphene mem-
brane. We want to emphasize that the switchable separation property
of MNG is attributable to the fast interlayer structure modulation of
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Fig. 6 | MNG membrane for binary dye mixture separation under dead-end
filtration. The test was conducted at 3 bar and dilution was conducted with 100 mL
of IPA. The total concentration was 1000 ppm in IPA and the weight ratio of the
dyes was 1:1. a Schematic illustration of binary dye mixture separation. The colored
square and circle are dye molecules. b Photographs of feed, re-dispersed retentate,
graphene by solvents. Indeed, the solvent exchange during the test
was conducted immediately after filtering solvent, so this phenom-
enon is more close to switching of MWCO by solvent type while solvent
swelling in the graphene channel is the origin of the switching
phenomena.
A steered MD simulation approach was employed to investigate
the change in the thermodynamic free energy, i.e., the potential of
mean force, as a solvent permeates through the graphene layers. This
thermodynamic quantity represents the solvent molecule perme-
ability within the graphene layers. Figure 8a depicts snapshots per-
taining to the observed behaviors of solvent molecules and graphene
layers during the steered MD simulations. The model utilized herein is
based on a pristine graphene layer. While graphene oxide or reduced
graphene oxide possess oxygen-containing groups or defective sp3
carbon regions, which are known to affect solvent permeation through
interaction or steric hindrance23,24, it is straightforward to understand
intrinsic solvent permeation through the graphene channel when
pristine graphene spacing is considered. In addition, the effect of
nanopores is disregarded because nanopores with dimensions of
several nanometers are sufficiently large to permit solvent permeation,
and the primary resistive channel is the narrow interlayer spacing of
stacked graphene.
Nature Communications | (2023)14:901
https://doi.org/10.1038/s41467-023-36524-x
and permeate solutions after each filtration cycle. c UV–Visible absorbance spectra
of AR, MO, and their mixture solutions in IPA. d, e UV–Visible absorbance spectra of
re-dispersed retentate and permeate solutions after each filtration cycle. f, g Purity
and concentration of AR and MO in the re-dispersed retentate and permeate
solutions after each filtration cycle.
As depicted in the snapshots, the solvent molecule permeability
strongly depends on the solvent identity and interlayer spacing. Water
and toluene tend to cluster at a d-spacing of 6.4 Å, exhibiting multiple
distributions of locally overlapping graphene layers. This can be
attributed to the Connolly-analyzed diameters of water (3.37 Å) and
toluene (3.83 Å) molecules, which are larger than the accessible
interlayer spacing (3.0 Å) calculated under the condition of the van der
Waals diameter (3.4 Å) of graphene carbon (Supplementary Fig. 28).
Therefore, the graphene layers swell to create a local space for the
solvent molecules, while the graphene layers locally overlap to com-
pensate for the swollen space. The Connolly-analyzed diameter of
toluene is assumed to be identical to methane because aromatic rings
of toluene molecules are positioned parallel to the graphene layers.
Using identical reasoning, the solvent molecules become well dis-
tributed throughout entire graphene layers as the layer spacing
increases at d-spacings of 7.4, 8.4, and 13.4 Å, which correspond to the
accessible interlayer spacings of 4.0, 5.0, and 10.0 Å, respectively
(Supplementary Fig. 28). No local overlapping of the graphene layers is
observed at these interlayer spacings. Consequently, these solvents
have significantly higher potentials of mean force at the layer spacing
of 6.4 Å compared to larger interlayer spacings, as shown in Fig. 8b,
indicating the highest resistance against the solvent permeation at the
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Fig. 7 | Switching MNG membrane performance for ternary dye mixture
separation under dead-end filtration. a Schematic image of ternary dye mixture
separation. The colored square, circle, and triangle are dye molecules. b UV–Visible
absorbance spectra and photographic images of feed and permeate solutions. The
layer spacing of 6.4 Å. Using the same reasoning, the minimum layer
spacing at which ethanol molecules homogeneously pass through non-
overlapping graphene layers is determined to be 8.4 Å, considering
the Connolly-analyzed diameter (4.79 Å) of ethanol. Therefore, the
potentials of mean force at the interlayer spacings of 6.4 and 7.4 Å are
significantly greater compared with those at layer spacings of 8.4 and
13.4 Å. Conclusively, these results combinedly imply that the perme-
ability of solvent molecules would be significantly enhanced at inter-
layer spacings with a free volume that can accommodate solvent
molecules without any swelling behaviors of graphene layers, as indi-
cated in green in Fig. 8a.
Further comparison of potentials of mean force at the interlayer
spacing of 13.4 Å for all three types of solvents reveals that toluene has
the highest resistance to solvent permeation, while ethanol exhibits
the least resistance (Fig. 8c). As depicted in Fig. 8d, the simulated
interaction energies between graphene layers and solvent molecules
Nature Communications | (2023)14:901
https://doi.org/10.1038/s41467-023-36524-x
total concentration was 10 ppm in IPA and the weight ratio of the dyes was 1:1:1. The
test was conducted at 3 bar. The feed solvent was IPA. Ethanol and NMP were used
for second and third filtration respectively.
demonstrate that the aforementioned difference in the potentials of
mean force would result from the difference in the interaction energy,
which follows the order of toluene < water < ethanol. Note that a larger
negative interaction energy value results in stronger interaction
between graphene layers and solvent molecules. Consequently, the
van der Waals-based strongest interaction between graphenes and
aromatic rings in toluene molecules leads to the strongest resistance
against the solvent permeation, whereas stronger hydrogen bonding
characteristics in water molecules would result in a stronger resistance
of water relative to ethanol against solvent permeation. The simulation
results imply that a larger interlayer spacing than the size of the solvent
is critical to achieving high solvent permeation through graphene
nanochannels, and that permeation can be further enhanced by
modifying the graphene surface with low interaction energy while
maintaining the same interlayer spacing. It is expected that the tur-
bostratic nanochannel of the proposed graphene membrane is one of
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Fig. 8 | Steered MD simulation of solvent permeation in graphene layers.
a Snapshots of solvents (water, toluene, and ethanol) passing through graphene
layers with various d-spacings. b Potentials of mean force displayed as a function of
the center of mass of solvent molecules for the steered MD simulations described in
the reasons for an ultrafast solvent flux, despite the fact that the
swelling degree of different solvents is generally uncontrollable in
experiments, unlike the simulation model.
Discussion
This study demonstrates the easy fabrication of nanoporous gra-
phene with high crystallinity by combining thermal activation and
microwave treatment. Previous reduction methods, such as chemical
reduction, are unable to restore the hexagonal lattice of defective
and oxidized graphene. However, microwave treatment is highly
effective for regenerating hexagonal carbon lattice as maintaining
nanoporous structure. In addition, the treatment process only
requires a few seconds, which is desirable for the future scalability of
Nature Communications | (2023)14:901
https://doi.org/10.1038/s41467-023-36524-x
a. c Potentials of mean force of water, toluene, and ethanol at a d-spacing of 13.4 Å.
d Interaction energy between graphene layers and solvents within the d-spacing
of 13.4 Å.
nanoporous graphene membrane. Using graphene as a building
block, a nanoporous multilayer graphene membrane with ultrafast
solvent permeation and switchable rejection performance was
developed. By recovering the sp2 carbon structure from sp3 carbons
through microwave treatment, an enhanced ordered interlayer
structure with dense nanopores can be produced. Consequently, the
membrane exhibited flexible and narrow MWCO owing to the swel-
ling degree of interlayers depending on the solvent type. Further-
more, the membrane was demonstrated to feasibly perform the
separation of multiple molecular mixtures, which can be utilized for
chemical extraction and concentrations in various application fields,
including petrochemicals and pharmaceuticals. Further, the pro-
posed graphene preparation methods can be applied to sensors,
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energy storage devices, adsorbents, and electrocatalysis, all of which
require a high surface area and electrical conductivity.
Methods
Synthesis of NG powder
GO powder was prepared using a modified Hummers’ method as
described in our previous studies48. First, 2 g of graphite powder was
dissolved in 150 mL of sulfuric acid. Second, 7 g of potassium per-
manganate (KMnO4) was slowly added to the graphite dispersion and
stirred at 35 °C for 5 h in a water bath. After stirring, 200 mL of deio-
nized (DI) water was slowly added to the dispersion in an ice bath.
Subsequently, 100 mL of hydrogen peroxide (H2O2) was poured into
the solution. The products (GO) were washed and filtered several times
with DI water to remove the remaining chemicals. Finally, GO powder
was obtained by freeze-drying. The prepared GO powder was loaded
into a quartz tube, which was then placed into a furnace set to 200 °C.
The GO powder was thermally annealed in the furnace at 200 °C under
ambient conditions for 5 min to activate nanopores. The activated
powder, NG, was collected after cooling to room temperature in air.
Production of MNG membrane
The as-prepared NG powder was placed into a commercial microwave
oven. The NG powder was treated at 700 W for 2 s. The resultant MNG
powder was collected and dissolved at a concentration of 0.5 mg/mL in
NMP. The solution was dispersed using a horn-sonicator (Sonic VCS
505) in an ice bath for 300 min. The obtained MNG solution was cen-
trifuged at 5400 × g (7000 rpm) for 30 min to remove large and
undispersed particles, and the dispersed MNG solution was collected
from the supernatant. The as-prepared MNG solution was diluted with
deionized water and subsequently filtered through nylon support
(Whatman, 0.2 µm pore size). After filtration, the MNG membranes were
dried in an oven at 60 °C overnight to eliminate any leftover solvents.
Binary dye mixture separation using a dead-end system
100 mL of feed solution containing methyl orange (MO; 327.33 g·mol−1)
and acid red 1 (AR; 509.43 g·mol−1) dyes (1:1 weight ratio) at a total
concentration of 1000 mg/L in IPA was filtered through an MNG
membrane using a homemade dead-end cell until the entire filtration
of the solvent. Next, 100 mL of pure IPA was introduced to the dead-
end cell to re-disperse the retentate, and the solution was filtered
again. The process was repeated 12 times. The concentrations of feed,
permeate, and re-dispersed retentate solutions were calculated using
UV–Vis spectroscopy.
Ternary dye mixture separation using a dead-end system
Under the dead-end condition, 100 mL of feed solution containing
methyl orange (MO; 327.33 g·mol−1), acid red 1 (AR; 509.43 g·mol−1),
and Evans blue (EB; 960.8 g·mol−1) dyes (1:1:1 weight ratio) at the total
concentration of 10 mg/L in IPA was filtered through the MNG mem-
brane. After the completion of solvent filtration, 100 mL of pure
ethanol was added to the dead-end cell to re-disperse the retentate.
Subsequently, the solvent was filtered. After adding 100 mL of pure
NMP to the cell to re-disperse the retentate, the solvent was filtered
again. This process of solvent exchange was repeated once more. The
solvent exchange process was conducted immediately after each
completion of solvent filtration.
Computational methods
The molecular dynamics (MD) simulation approach was employed to
investigate the permeation behaviors of solvent molecules passing
through the graphene layers. First, each periodic simulation model was
initially prepared to contain graphene layers with solvent molecules
occupying space between the layers. Either toluene, water, or ethanol
was introduced as a solvent in each simulation model. The prepared
models were then equilibrated by a series of NVT (298 K) and NPT
Nature Communications | (2023)14:901
https://doi.org/10.1038/s41467-023-36524-x
(298 K and 1 atm) ensembles for 5 ns to have graphene layers with a
targeted layer spacing in which space between graphene layers was
filled with solvent molecules. Four distinctive layer spacings, namely
6.4, 7.4, 8.4, and 13.4 Å, were introduced for each solvent case to
identify suitable layer spacings for the facilitated solvent permeation.
Nose–Hoover thermostat and barostat were used to control the tem-
perature and pressure under the condition of the NPT ensemble,
respectively. All these simulations were performed using the LAMMPS
simulation package with the DREIDING force field49,50. Next, a steered
MD simulation approach implemented in the LAMMPS simulation
package was performed to predict free energy changes associated with
the behaviors of solvent molecules passing through the graphene
layers. Note that the steered MD simulation approach is suitable to
understand the thermodynamic preference of the designated path-
ways of solvent molecules. During the steered MD simulations, a spring
constant of 1000 kcal/mol/Å and pulling velocity of 10−5 Å/fs were
applied to solvent molecules in the simulation models while graphene
layers were not presumed to be pulled out. The free energy profiles of
the solvent molecules passing through the space between graphene
layers during the steered MD simulations were recorded in form of the
potential of mean force (PMF). All the steered MD simulations were
performed under NPT (298 K and 1 atm) ensemble for 1 ns.
Data availability
The data supporting the findings of this study are available within the
paper and Supplementary Information. Any additional detail can be
requested from the corresponding authors.
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Acknowledgements
This work was supported by the National Research Foundation of Korea
(NRF) grant funded by the Government of South Korea (MSIT) (NRF-
2020R1C1C1003289), and the Technology Innovation Program
(20013621, Center for Super Critical Material Industrial Technology)
funded by the Ministry of Trade, Industry & Energy (MOTIE, South Korea).
This research was supported by basic science research program
through the National Research Foundation of Korea funded by the
Ministry of Education (NRF-2019R1A6A1A11055660).
Author contributions
J. Kang performed the experiments and collected the data. Y.K. and
K.C.K. performed computational simulation. J.P.K., J.Y.K., J. Kim, and
O.K. assisted in data analysis. J. Kang and D.W.K. prepared the manu-
script. The project was conducted under the supervision of D.W.K. All
subjects gave their informed consent for inclusion before they partici-
pated in the study.
Competing interests
The authors declare no competing interests.
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Article
Additional information
Supplementary information The online version contains
supplementary material available at
https://doi.org/10.1038/s41467-023-36524-x.
Correspondence and requests for materials should be addressed to Dae
Woo Kim.
Peer review information Nature Communications thanks Suzana Nunes
and the other, anonymous, reviewer(s) for their contribution to the peer
review of this work.
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